High molecular weight substituted ethinyl carbinols



bromide, upon ketones.

Patented June 4, 1940 own-.1)? ST TES PATENT OFFICE Anderson W.

" "mention-zooms WEIGHT SUBSTITUTED Q n'rmm CARBINOLS Balaton, Chicago,7 111., assignor to Armour and Company, Chicago, 111., a corporation ofIllinois No Drawing. Application Ma y 2 3, 193 8 sfil'ill N0. 209,605 I5 Claims. (01.260-632) This invention relates high molecular. weightsubstituted ethinyl carbinols and it comprises 10 compounds ofexceptional scientific and commercial interest. Because of their highdegree of unsaturation combined with the presence of the hydroxyl groupthey can be polymerized i 'readily'to' resins and plastics. They arealsouseful for incorporation into various plastic compositions in orderto impart plasticity thereto. Low molecular weight substituted ethinylcarbinols have been prepared by the action of Grignard reagents, such asacetylene magnesium This method has not applied to the preparation ofhigh .rnolecu- :lar weight ethinyl carbinols. A commerciallysatisfactory method of preparing high molecular weightsubstitutedethinyl carbinols would make such compounds available forwide usesin the plastic andgresin fields. I, a. I l

I have discovered that high molecular weight ethinyl carbinols of thegeneral formula I have found that this reaction proceeds smoothly inliquid ammonia and other non-aqueous solvents. When liquid ammonia isemployed as the solvent it is not necessary to isolate the metalacetylide from the ammonia solution in which it is formed but it can bereacted directly with the ketones and the end product of the reactionisolated. The following examples can be given as illustrative of myinvention:

The most E u? I .11,1-ditridec1 l-Z-propyn-1-0l Two andthree-tenthsgrams of sodium are added to 75 cc. ogliquid ammonia and suflicientacetylene added "to discharge the blue color. Seven and seven-tenthsgrams of myristone are then suspended in about 50 "cc. of liquidammonia, the mixture added to the ammonia solution' of the acetylide andthe whole maintained in asteelbomb. Thebomb is closed and the 1.temperature allowed to rise to room temperature. The reaction mixture iskept under pressure at room'temperature for a period of about 48 hourswith occasional shaking. The pressure is then released and the amrnoniaevaporated. The rell action product is then hydrolyzed with ice, theaqueous mixture .filtered, and the filter cake dried. The crude productis next dissolved in 150 :cc. of. acetone and the acetone solutionfiltered. The acetone is finally evaporated and go a residue of 5 gramsof 1,1-ditridecyl-2-propyn- 1-ol obtained. compound can be recrystal- 1lized-from alcohols It'is a waxy 'solid melting at 34-35 C.', and upondistillation it decomposes into myristone and acetylene. F ExmPLE2 V gLI-diundecul-Z-zrropzIn-I-ol Two and three-tenths grams ofsodium arereacted with acetylene in ammonia to give ethinyl a sodium according toExample 1. Eight and fivetenths grams of laurone suspended in about 50cc. of liquid ammonia are then added and the whole placed in a steelbomb. The bomb is then closed and allowed to stand for 18 hours at roomtemperature with occasional shaking. The pressure is then released, thecontents poured onto ice and then filtered. The cold, solidified filtercake is dissolved in acetone and the acetone evaporated. Six andfive-tenths grams of 1,1- diundecyl-Z-propyn-l-ol are obtained, which isa liquid boiling at 210-215 C. at 3 mm. with slight decomposition intolaurone and acetylene. 1,1-diundecyl-2-propyn-1-ol is also obtained bythe reaction of ethinyl sodium with laurone using ether as the solvent.After 4 days at room temperature a yield of 4 grams of 1,1-diundecyl-2-propyn-1-ol is obtained from 8.5 grams. of laurone starting material.

Exurru: 3 1,1-diheptadec1 l-2-propun-1-ol' Two and three-tenths grams ofsodium are converted to ethinyl sodium and reacted with 10 grams ofstearone in liquid ammonia. The reaca tion is allowed to proceed underpressure for 40 hours at room temperature, after which the reactionmixture is poured upon ice, the aqueous mixture filtered and the solidfilter cake taken up d in acetone. It is recrystallized from alcohol and7.5 grams oi- 1,1-diheptadecyl-2-propyn-l-ol obtained. This is awax-like solid melting at 58-59" C.; It cannot be distilled withoutdecomposition into stearone and acetylene.

Emirate 4 I I 1-diphenyl-1-heptadecul-M mm-1-ol Two and three-tenthsgrams of sodium are converted to ethinyl sodium according to the methoddescribed under Example 1. This is then reacted for hours with 8.4 gramsoi. diphenyl heptadecyl ketone suspended in cc. of liquid ammonia. Thereaction is conducted in a steel F bomb at atmospheric temperatures.After hydrolysis tour and five-tenths grams ofl-diphenyl-l-heptadecyl-propyn-l-ol are obtained which melts at fig- C.after recrystallizationhrom alcohol.

Exams: 5

1,1-diundecyl-3-vinyl-2-propyn-1-ol Ten grams of laurone are reactedwith 3.1 grams of sodium vinyl acetylide in liquid ammonia for 18 hoursunder pressure at' room tem- "1 perature. The product is treated asdescribed under Example 1. Eight and five-tenths grams ofl,1-diundecyl-3-vinyl-2-propyn-1-ol are obtained. This is a yellowish,viscous liquid which can be polymerized to a solid by heating.

. Exams: 6

1,1,4,4-tetraundecz l-z-butzm-Ll-diol Five and two-tenths grams ofsodium carbide are suspended in liquid ammonia and 17 grams of lauronedissolved in liquid ammonia added. The reaction is conducted in a steelbomb which is sealed and allowed to remain under pressure at roomtemperature for 40, hours. The mixture is then poured onto iceand-extracted with acetone. Twelve and five-tenths grams of1,1,4,4-tetraundecyl-2-butyn-l,4-diol are obtained. 1,13,4-tetraunde'cyl-Z-butyn-1,4-diol is a solid melting at -111 C.

conditions.

asoases The same product is obtained in, somewhat smaller yields whenlaurone and sodium acetylide react in liquid ammonia at roomtemperatures in; the presence oitrimethyl lead chloride. I do notattempt to explain its formation under these When laurone isreactedwithsodium'acetyllde using ether as a solvent and in the absencec1 lead compounds the greater percentage of the product is1J-diundecyl-Z-propyn-l-ol. However, a small amount, or the order or10%, oi the diol is also formed.

' Having thus described my invention, what I claim is:

1. Acetylenic compounds containing the groupi118 c-c =.ox in on vwherein R a anm maimconaunmg-at least ten carbon atoms, R is a radicalchosendrcm the group consisting of alkyl radicalscontainins at least tencarbon atoms and aryl radicals, and

X is a radical chosen'trom-the srollniconsl t nfi of hydrogen, an alkylradical and the radical ./Q won wherein R and R are radicals deiinedasstore-Q said. .7 .5 1 v I 2. Acetylenic compounds of thegeneraidor mulac-o:o+c

a, on Y on a.

wherein R is alkyl radical chat least ten carbon atoms and R1 1 is'chwen iromutheg'roup consisting of alkyl radicals oi at least' tencarbon atoms and aryl radicals.1 a

3. 1,1-ditridecylJ-propynl-ol. 4. 1,1-diheptadecyl-2-propyn+1eol... 5.1,1,4,4-tetraundecyl-2*butyn--1,4- diol.

